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CN1434066A - Continuous Production of Thermoplastic Polyurethane Elastomers - Google Patents

Continuous Production of Thermoplastic Polyurethane Elastomers Download PDF

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Publication number
CN1434066A
CN1434066A CN03101081A CN03101081A CN1434066A CN 1434066 A CN1434066 A CN 1434066A CN 03101081 A CN03101081 A CN 03101081A CN 03101081 A CN03101081 A CN 03101081A CN 1434066 A CN1434066 A CN 1434066A
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CN
China
Prior art keywords
tpu
diisocyanate
polyurethane
thermoplastic polyurethane
prepolymer
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Pending
Application number
CN03101081A
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Chinese (zh)
Inventor
W·布罗伊尔
H·海丁斯费尔德
H·－G·霍佩
W·考夫霍尔德
B·舒尔特
J·C·陈
S·C·曼宁
N·R·纳多
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Bayer AG
Bayer Corp
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Bayer AG
Bayer Corp
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Publication of CN1434066A publication Critical patent/CN1434066A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a continuous process for preparing thermoplastic polyurethane elastomers. The method is implemented at 130-250 ℃, and comprises the following steps: at least one polyether diol is reacted with at least one organic diisocyanate, and 1, 4-bis- (2, 2' -hydroxyethyl) -hydroquinone in the presence of tin dioctoate as catalyst. Glass transition temperature (T) of the resulting thermoplastic polyurethaneg) Below 50 ℃. The thermoplastic polyurethanes of the invention are suitable for the production of injection-molded or extrusion-molded articles.

Description

The continuous production of Polyurethane Thermoplastic Elastomer
Technical field
But the present invention relates to continuous, catalysis process that a kind of employing aromatic chain extenders is produced thermoplastic machined polyurethane elastomerics (TPU).More particularly, TPU demonstration of the present invention is lower than 50 ℃ second-order transition temperature (T g).
Why the Application Areas of thermoplastic polyurethane (TPU) extensively is because they show superior elasticity bulk properties and their further thermoplastic processing easily.The summary of one piece of relevant TPU, its characteristic and application thereof for example is published in: " plastics " 68 (1978) 819; " rubber, caouttchouc and plastics " 35 (1982) 569; And " plastics handbook G.Becker, D.Braun chief editor, volume 7, " urethane " Munich, vienna, Carl Hanser press 1983.One piece of summary about production method is stated from " plastic molding press " 40 (1989).
Most of TPU are that preferred two functional alcohol constitute by the line style polyvalent alcohol such as the pure and mild polyether glycol of polyester polyols, organic diisocyanate with as the short chain alcohol of chain extension agent.This type of TPU both can be by intermittently also can be by continuous mode production.
Generally speaking, chain extension agent is a short-chain diol, is aliphatic diol mostly, for example comprises ethylene glycol, butyleneglycol and hexylene glycol.Utilize few chains of aromatic of using to increase chain, for example, utilize the thermoplastic polyurethane of the hydroxyl alkylene ether of quinhydrones to have the advantages that thermostability is high especially, elasticity is very high and compression set is low.
But a kind of thermoplastic processing mollielast that is particularly suitable for making softness, adhesion film is described among the EP-A-0 308 683.It is made by mixed polyester (molecular weight 1800～3600) and organic diisocyanate and aromatic diol chain extension agent.This kind TPU preferably adopts stannous octoate (tin) or two lauric acid tin to make in the time at several minutes as catalyzer by single stage method in the reactor of 110～140 ℃ of beginning temperature.
The hard TPU that a kind of second-order transition temperature based on special aromatic chain extenders is at least 50 ℃ is disclosed in United States Patent (USP) 5,574, in 092.During fabrication, adopt step interrupter method production, 80～100 ℃ of starting temperatures adopt 0.02～2wt% catalyzer such as organo-tin compound.Unexposed duration of contact.Prepared TPU makes sheet material and cooling through curtain coating.
Two kinds of methods described above neither be fit to, produced TPU economically, because their duration of contact is long and/or their running cost is high.
A kind of continuation method of making TPU under the reactor medium and high temperature of two combine operationss is disclosed in United States Patent (USP) 5,795, in 948.This method is allowed and is made TPU economically.This program requires the rapid technology of multistep, the first step wherein, and polyvalent alcohol mixes with vulcabond.In second step, a kind of isocyanic ester terminated prepolymer is in reactor, greater than generating under 100 ℃ the temperature.In the 3rd step, this prepolymer and molecular weight mix between 62～500 chain extension agent glycol.In the 4th step, be reflected in second reactor and under high shear forces, finish.Polyester is in an embodiment as polyvalent alcohol, and butyleneglycol is as chain extension agent.The combination of mentioning employing stirring pipe reactor and twin screw extruder especially is as reactor.
Yet if aromatic chain extenders and this general T PU catalyzer, for example, titanium catalyst at United States Patent (USP) 5,795, is used in combination in the disclosed program in 948, and the result will obtain the low heterogeneity product of a kind of performance.In addition, in the melt filtration of routine, also usually go wrong.
United States Patent (USP) 6,022,939 is open by vulcabond and polyethers and contain the benzene of replacement and the chain extension agent mixture of alkanediol prepares the method for TPU at dibutyl tin laurate as reacting in the presence of the catalyzer.This product is taked the intermittent mode manufacturing, and duration of contact is greater than 1h.Yet, create conditions down at quantity-produced, owing to the reduction that causes degree of crystallinity because of the interference of second chain extension agent, the result obtains a kind of heterogeneity, is clamminess to the product that is difficult to remove again.
Summary of the invention
But the purpose of this invention is to provide a kind of production and have high thermal stability and the elastomeric continuous and economic method of very elastomeric thermoplastic machined polyurethane.This purpose is to adopt the specific combination of reactive component and reaction parameter to realize.
The present invention relates to a kind of carry out at 130～250 ℃, preparation second-order transition temperature (T gBut) being lower than the continuation method of 50 ℃ thermoplastic machined polyurethane elastomerics (TPU), this method comprises to be made:
A) at least a polyether glycol on average has the number-average molecular weight (M of 1.8～2.2 Zerewitinoff active hydrogen atoms and 450～10,000 n),
B) at least a organic diisocyanate, and
C) 1,4-two-(2,2 '-hydroxyethyl)-quinhydrones
10～1,000ppm is a benchmark with polyethers (A), the existence of two stannous octoates as catalyzer under react, condition is, A), B) and NCO/OH ratio C) between 0.85～1.2.
So the TPU of preparation can randomly be included as auxiliary or the auxiliary agent that reaches technical separately generally acknowledged function and add.Any mixture of aliphatic series, cyclic aliphatic, araliphatic, aromatics and heterocycle vulcabond or these vulcabond all can be used as organic diisocyanate (B), and (suitable vulcabond is disclosed in HOUBEN-WEYL " organic chemistry method " volume E2-" macromolecular substance ", Georg Thieme press, the Stuttgart, New York 1987, pp.1587～1593; " Justus Liebigs Anomalies of Chemistry " 562 pages, receives for referencial use at this with these two pieces in the lump by 75～136 pages).
Example comprises that aliphatic vulcabond is as two isocyanic acid ethylidene esters, two isocyanic acid tetramethylene esters, two isocyanic acid hexamethylene esters, 1,12-dodecane vulcabond; Cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexyl diisocyanate, 1-methyl-2,4-cyclohexyl diisocyanate and 1-methyl-2,6-cyclohexyl diisocyanate, and even corresponding heterogeneous mixture, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 '-dicyclohexyl methane diisocyanate and 2,2 '-dicyclohexyl methane diisocyanate, and even corresponding heterogeneous mixture; In addition, suitable has aromatic diisocyanate as 2,4-toluylene group diisocyanate, 2,4-toluylene group diisocyanate and 2, the mixture, 4 of 6-toluylene group diisocyanate, 4 '-'-diphenylmethane diisocyanate, 2,4 '-'-diphenylmethane diisocyanate and 2,2 '-'-diphenylmethane diisocyanate, urethane-modified liquid state 4,4 '-'-diphenylmethane diisocyanate or 2,4 '-'-diphenylmethane diisocyanate, 4,4 '-two isocyanato-diphenylethanes-(1,2) and 1, the 5-naphthalene diisocyanate.Preferred isocyanic ester is 1,6-hexylidene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, the heterogeneous mixture of '-diphenylmethane diisocyanate, wherein 4,4 '-'-diphenylmethane diisocyanate content is greater than 96wt%, and especially 4,4 '-'-diphenylmethane diisocyanate and 1, the 5-naphthalene diisocyanate.Given vulcabond both can also can form of mixtures each other use separately.They also can use with the highest 15mol% (is benchmark by total vulcabond) polyisocyanates, but only have at most so many polyisocyanates to add, but the product thermoplastic processing still that obtains with toilet.The example of polyisocyanates is a tritane-4,4 ', 4 "-triisocyanate and many phenyl-polymethylene polyisocyanates.
Reactant (A) comprises at least a polyether glycol, and it on average has the number-average molecular weight (M of 1.8～2.2 Zerewitinoff active hydrogen atoms and 450～10,000 n).
Suitable polyether glycol can be by having one or more oxyalkylenes of 2～4 carbon atoms in alkene (or alkylidene group) residue, and the reaction that comprises between the startup molecule of two active hydrogen atoms prepares.Oxyalkylene, that can enumerate as an example has: oxyethane, 1,2 epoxy prapane, Epicholorohydrin and 1,2-butylene oxide ring and 2,3-butylene oxide ring.Oxyethane, propylene oxide, and the mixture of 1,2 epoxy prapane and oxyethane is preferred the use.Oxyalkylene can use respectively also and can form of mixtures each other use.The example that starts molecule comprises water, amino alcohol such as N-alkyl diethanolamine, for example, and N-methyl-diethanolamine and such as ethylene glycol, 1, ammediol, 1,4-butyleneglycol and 1, the glycol of 6-hexylene glycol and so on.Randomly, also can use the mixture that starts molecule.
Other suitable polyether glycols are polymerisates of the tetrahydrofuran (THF) of hydroxyl group.Also can use 0～30wt%, be benchmark in two functional polyethers glycol, the trifunctional polyether triol, yet, but its highest consumption is with the product that guarantees to be generated still thermoplastic degree of being processed as.The substantial linear polyether glycol that preferably on average has the number-average molecular weight (Mn) of 1.8～2.2 Zerewitinoff active hydrogen atoms and 450～6,000.They both can use respectively also and can form of mixtures each other to have used or to use with the form of mixtures of polyester glycol.It also is a kind of selection that polyester glycol substitutes polyether glycol.
Monofunctional compound can be used as so-called chain terminator, and its consumption is up to 2wt%, for TPU.For example, suitable those are monoamines, as butyl and dibutylamine, octyl amine, octadecylamine, N-methyl octadecylamine, tetramethyleneimine, piperidines or hexahydroaniline, monohydroxy-alcohol such as butanols, 2-Ethylhexyl Alcohol, octanol, dodecanol, Stearyl alcohol, various amyl group alcohol, hexalin and ethylene glycol monomethyl ether.
Compound (A) and relative populations (C) be chosen as total isocyanate groups number of making in (B) and (A) and the ratio between the total isocyanate-reactive hydrogen atom number (C) between 0.85: 1～1.2: 1, more preferably 0.95: 1～1.1: 1.
Two stannous octoates are used as catalyzer, and its consumption is between 10～1,000ppm, and preferred 50～300ppm is for polyethers (A).
Polyurethane Thermoplastic Elastomer of the present invention can comprise those its known auxiliary substance of function or auxiliary agent in TPU, and the highest 20wt% of consumption is for the TPU gross weight.Typical auxiliary substance or assistant packet are stablizer and various element, softening agent, antiblocking agent, inhibitor, lubricant and releasing agent, the material with fungicidal and bacteriostatic action and inorganic and/or organic filler and composition thereof of dyestuff, pigment, flame-proofness, toughener, anti-aging influence (for example, anti-hydrolysis, illumination, heat and variable color).
The example of lubricant is fatty acid ester, its metallic soap, fatty acid amide, aliphatic ester acid amides and silicone compounds.Toughener is fiber reinforced material especially, as, inorganic fibre was randomly handled with lubricated stripper.About the more details of optional auxiliary substance above-mentioned and auxiliary agent can be referring to technical literature, for example, receive monograph for referencial use: J.H.Saunders and K.C.Frisch, be entitled as " high polymers " volume XVI, " urethane " part 1 and 2, international scientific press publishes respectively at 1962 and 1964; " the plastics additive pocket book " of R.Gaechter and H.Mueller (Hanser press, Munich 1990); And DEA29 01 774.
Other additives that can join among the TPU are thermoplasticss, for example, and polycarbonate and acrylonitrile-butadiene-styrene (ABS)-terpolymer, particularly ABS.Other elastomericss such as rubber, ethylene/vinyl acetate multipolymer and styrene/butadiene copolymers and even other TPU can use too.
Continuous production process of the present invention is implemented 130～250 ℃ temperature.In this program, before the reaction beginning, raw material polyethers A) and glycol C) being heated to 130～230 ℃, organic diisocyanate is heated to 50～150 ℃.Reaction end owing to be thermopositive reaction, will reach 180～250 ℃.
TPU of the present invention can make according to conventional hybrid head/belt program or so-called forcing machine program.In the forcing machine program, for example, in multiple screw extruder, component A), B) and feeding C) can carry out simultaneously, in other words in the single stage method program, perhaps one by one, in other words according to a kind of prepolymer program.In this way, both also preparations serially off and on of prepolymer.In continuous prepolymer process, prepolymer is to be arranged in prepolymer unit (aggregate) manufacturing that the front is polyphone in the first part of forcing machine or independent.This kind prepolymer unit can be stirred tube reactor or one or more tactic static mixer.
According to the TPU of continuous prepolymer program manufacturing is preferred, and especially preferred be the prepolymer program of in forcing machine, carrying out.
From reaction begin to its finish and the total reaction time that obtains the TPU melt between 0.3～3min, preferred 0.5～2min.
The TPU melt of preparation preferably utilizes the filter sieve of mesh size 30～300 μ m to filter at the exit end of forcing machine.
TPU of the present invention can further process, for example, polymkeric substance can bar or bulk form be in harmonious proportion, in pulverizer or mill, pulverize or granulation, outgas and even take advantage of the molten state granulation.Preferably, polymkeric substance is conducted through the unit (aggregate) of a continuous degassing and the shaping of line material.As this kind unit (aggregate), can be only to be equipped with a few to mediate key element (kneader), the randomly basic not multiple screw extruder of kneading effect.
High temperature of the present invention, short residence time(SRT) continuous process can be produced the such class TPU with special overall characteristic.
The TPU that makes according to program of the present invention is homogeneous very, has extraordinary machinery and elastic performance and is feature with its high thermal stability.TPU can be used in injection-molded item and the extrusion molding made in accordance with the present invention.So the injection molding sheet material quality of making all has extraordinary mechanical property in the lump.
The present invention will further specify by the following examples, but be not limited thereto, and wherein all umbers and percentage number average refer to weight, unless point out separately.
Embodiment
Prescription 1 (example 1,3～5)
62.1 weight part (pbw) polybutylene oxide (number-average molecular weight about 1000) and four (3 (3 of 0.1 weight part tetramethylolmethane, 5-to-1, the 1-dimethyl ethyl)-and the 4-hydroxyphenyl) propionic ester and corresponding catalyst (referring to form) be heated to beginning temperature separately together, produces a kind of mixture.This mixture is fed in the online static mixer (Sulzer DN50) of 3 polyphones continuously.Meanwhile, 28.4 weight parts 4,4 '-'-diphenylmethane diisocyanate (60 ℃) is pumped in this static mixer.
The prepolymer that obtains is fed into forcing machine (Werner ﹠amp; Pfleiderer; ZSK 120) first opening for feed in, 9.4 weight parts 1 simultaneously, 4-two-(2,2 '-hydroxyethyl)-quinhydrones adds continuously by opening for feed 3.The speed of rotation of screw rod is 240rpm.
At the discharge end of forcing machine, melt is accepted the filtration of the insert metallic screen of mesh size 200 μ m, extrudes cooling and granulation in water-bath with line material form.
Prescription 2 (examples 2)
The other incoming flow that enters forcing machine (ZSK 120) is: the mixture (A) that A) passes through the opening for feed 1 of forcing machine:
61.9 weight part polybutylene oxide (number-average molecular weight about 1000)
0.1 four (3 (3,5-to-1,1-dimethyl ethyl)-4-of weight part tetramethylolmethane
Hydroxyphenyl) propionic ester
0.2 weight part hexylene glycol
Catalyzer (referring to form) B) opening for feed 1 of adding forcing machine
9.4 weight part 1,4-two (2,2 '-hydroxyethyl) quinhydrones C) adds the opening for feed 3 of forcing machine
28.4 weight part 4,4 '-'-diphenylmethane diisocyanate.
Prescription 3 (examples 6 and 7)
According to cooperating the program that adopts, but adopt following raw material to feed: four (2 (3,5-to-1,1-dimethyl ethyl)-4-of 42.1 weight part polybutylene oxides (number-average molecular weight about 1000), 0.1 weight part tetramethylolmethane with prescription 1
Hydroxyphenyl) propionic ester
Catalyzer (referring to form) 37.5 weight parts 4,4 '-'-diphenylmethane diisocyanate, 20.3 weight parts 1,4-two (2,2 '-hydroxyethyl)-quinhydrones
Sample is made in injection moulding machine (screw diameter 28cm-Kloeckner) by pellet.Measurement of hardness is according to DIN 53505, and tensile property is measured according to DIN 53504.
The result sums up in following table.The homogeneity of product and the filter screen operation lifetime that obviously prolongs are the outstanding advantages that adopts program of the present invention.Referring to form: tac representative's acetopyruvic acid titanium, SND represents two stannous octoates.
In relating to the quantity-produced embodiment of TPU, heterogeneous impurity passes through, for example, and melt filtration net (for example, at outlet of extruder) and filtering.Pressure before the melt filtration net raises in time.In case reach maximum allowble pressure, just need to change filter screen.(elapsed time is represented the filter screen operation lifetime before changing).Adopt program of the present invention, the heterogeneous thing of generation is quite few, so the filter screen operation lifetime is longer than when implementing known procedure greatly.
Very all show in the lump with the product that adopts the known procedure manufacturing according to the product of program manufacturing of the present invention and to compare improved mechanical property numerical value (ultimate tensile strength/elongation).
Table 1 has been summed up the condition that adopts in the TPU preparation, comprises TPU of the present invention (example 3,4,5 and 7) and those (1,2 and 6) of not belonging to the scope of the invention.
Table 1
Example Prescription Catalyzer/consumption (ppm) The beginning temperature, polyvalent alcohol (℃) The ZSK temperature (℃) Filter screen operation lifetime (hours) The injection moulding sample mass
?1 * ?1 ?TAC/10 ?180 ?180-220 ????0.3 ?HNH
?2 * ?2 ?TAC/10 ?195 ?180 ????0.3 ?NH
?3 ?1 ?SND/110 ?215 ?200-240 ????2 ?H
?4 ?1 ?SND/110 ?154 ?180-210 ????2 ?H
?5 ?1 ?SND/110 ?138 ?150-200 ????4 ?H
?6 * ?3 ?TAC/10 ?180 ?160-180 ????0.3 ?NH
?7 ?3 ?SND/110 ?160 ?160-180 ????2 ?H
HNH-represents the height heterogeneity, and H represents homogeneous, and NH represents heterogeneity * Comparative Examples, has summed up the performance of product not according to TAC-acetopyruvic acid oxygen titanium SND-two stannous octoate tables 2 of the present invention Table 2
Example Second-order transition temperature *??(℃) Shore hardness Rate of extension, tension test [mm/min] 100%-modulus [MPa] Tensile strength [MPa] Extension at break [%]
??1 * ??-46 ??84A ??50 ??6.4 ??38 ??400
??2 * ??-45 ??87A ??50 ??6.9 ??34 ??400
??3 ??-46 ??87A ??50 ??6.8 ??47 ??438
??4 ??-46 ??88A ??50 ??6.8 ??51 ??458
??5 ??-46 ??86A ??50 ??6.6 ??51 ??480
??6 * ??-19 ??63D ??500 ??23 ??36 ??347
??7 ??-19 ??60D ??500 ??27 ??39 ??393
* second-order transition temperature TG is from dynamic mechanical analysis (DMA)
Though the present invention has been described in detail for illustrative purposes above, but know, these details only for this purpose, those skilled in the art can therefrom make various conversion scheme under the condition that does not depart from spirit and scope of the invention, different is that the scope of the invention can be defined by the claims uniquely.

Claims (6)

  1. One kind 130～250 ℃ the preparation Polyurethane Thermoplastic Elastomer continuation methods, this method comprises: make,
    A) at least a polyether glycol on average has the number-average molecular weight (M of 1.8～2.2 Zerewitinoff active hydrogen atoms and 450～10,000 n); With
    B) at least a organic diisocyanate, and
    C) 1,4-two-(2,2 '-hydroxyethyl)-quinhydrones,
    10～1,000ppm is a benchmark with (A), the existence of two stannous octoates as catalyzer under react,
    Condition is reactant A), B) and NCO/OH ratio C) between 0.85～1.2, the second-order transition temperature (T of described thermoplastic polyurethane g) be lower than 50 ℃.
  2. 2. the process of claim 1 wherein to prepare and in forcing machine, carry out.
  3. 3. the process of claim 1 wherein to prepare and implement by prepolymer process.
  4. 4. the method for claim 2 wherein prepares by prepolymer process and implements.
  5. 5. according to the polyurethane elastomer of the method for claim 1 preparation.
  6. 6. the polyurethane elastomer of claim 5, it also contains at least a component that is selected from auxiliary substance and auxiliary agent.
CN03101081A 2002-01-09 2003-01-09 Continuous Production of Thermoplastic Polyurethane Elastomers Pending CN1434066A (en)

Applications Claiming Priority (2)

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US10/043738 2002-01-09
US10/043,738 US20030158365A1 (en) 2002-01-09 2002-01-09 Continuous production of thermoplastic polyurethane elastomers

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